To format for more than 2 Gigs you must use Win95B or Windows 98 or later with FAT32. The original WIN95A used something called FAT16 (16 binary bits = 65,536 clusters in the fat table) even with 32K in a cluster could only map 2 Gigs. The FAT32 (32 binary bits = 4,294,967,296 clusters in the fat table) with a 4K cluster that maps 17 terabytes and with a 32K cluster it maps 137 terabytes.
Now to tell which version you have - look at the command.com file in the root directory If it has a date of July 1995 it is Windows 95A. If it is 1996 or later it should be Win 95B or later and have the FAT32 built in.
The main computer is the only one that has to be upgraded to handle the larger drives.
There are many ways to divide the drives and load the data. You can leave them as a single partition, copy the CD's into sub directories and use the SUBST command in the autoexec.bat file. Or you can use tools like partition magic (see the bottom of the FHCTECH web page) to dynamically adjust the size of the partitions to match your needs.
The servers can run Windows 95B/98 Peer to Peer, Windows NT, Novell, Lantastic, others.
The workstations can run Windows 95A/95B/98/NT Workstation/Windows 3.11/ Dos 6.22 with Dos Client. A lot of this will be determined by the experience and expertise of the Computer Specialist or volunteer that is setting up the network and the resources available.